Synthetic K +-binding macrocycles have potential as therapeutic agents for diseases associated with KcsA K + channel dysfunction. We recently discovered that artificial self-assembled n-alkyl-benzoureido-15-crown-5-ether form selective ion-channels for K + cations, which are highly preferred to Na + cations. Here, we describe an impressive selective activation of the K + transport via electrogenic macrocycles, stimulated by the addition of the carbonyl cyanide-4-(trifluoromethoxy) phenylhydrazone (FCCP) proton carrier. The transport performances show that both the position of branching or the size of appended alkyl arms favor high transport activity and selectivity SK + /Na + up to 48.8, one of the best values reported up to now. Our study demonstrates that high K + /Na + selectivity obtained with natural KcsA K + channels is achievable using simpler artificial macrocycles displaying constitutional functions.